Polyether-urethane-urea additives for block resistance and open time

ABSTRACT

A hydrophilic polyurethane comprising polymerized units of: (a) a water-soluble polyol having hydroxyl functionality from two to four and a weight-average molecular weight from 800 to 16,000; and (b) an aliphatic polyisocyanate having isocyanate functionality from two to six; wherein polymerized ethylene oxide units comprise at least 85 wt % of said hydrophilic polyurethane; and wherein a product of weight fraction of polymerized ethylene oxide units and polyethylene oxide mean molecular weight is from 4,200 to 16,000.

FIELD OF THE INVENTION

The present invention relates to polyether-urethane-urea (PEUU) additives which improve open time in latex paints without having a substantial negative effect on block resistance.

BACKGROUND OF THE INVENTION

Hydrophobically modified urethane thickeners (HEURs), which are produced from polyisocyanates and/or diisocyanates and glycols, are known as water soluble polymers containing hydrophobic groups. They are classified as associative thickeners and frequently used in latex paint formulations, where the hydrophobic groups adsorb to latex particle surfaces, giving rise to viscosity increase and desirable rheological characteristics over a wide range of shear rates. For example, U.S. Pat. No. 4,079,028 discloses HEUR thickeners.

However, open time, defined as the period of time in which a freshly applied wet paint film can be repainted over without impeding film formation or changing the physical appearance, is often problematic in latex paints.

It would therefore be an advance in the art of latex paint formulation to improve open time without producing a substantial negative effect on block resistance.

SUMMARY OF THE INVENTION

The present invention is directed to a hydrophilic polyurethane comprising polymerized units of: (a) a water-soluble polyol having hydroxyl functionality from two to four; and (b) an aliphatic polyisocyanate having isocyanate functionality from two to six; wherein polymerized ethylene oxide units comprise at least 85 wt % of said hydrophilic polyurethane polymer.

DETAILED DESCRIPTION OF THE INVENTION

All percentages are weight percentages (wt %) and all temperatures are in ° C., unless otherwise specified. All operations are performed at room temperature (20-25° C.) unless otherwise specified.

As used herein, the term “water-soluble polyol” refers to one or more polyethylene oxides, water-soluble polyethylene oxide/polypropylene oxide copolymers, water-soluble polyethylene oxide/polybutylene oxide copolymers, water-soluble polyethylene oxide/polypropylene oxide/polybutylene oxide terpolymers and water-soluble polyols comprising polymerized units of C₃-C₈ triols (e.g., glycerol, trimethylolpropane) and polymerized units of at least one of ethylene oxide, propylene oxide and butylene oxide. As used herein, the term “water-soluble” means soluble in water at least to the extent of 10 wt %, based on total weight of solution (preferably 20 wt %). A used herein, the term “polyisocyanate” refers to an isocyanate source having at least two isocyanate groups per molecule. The term “aliphatic polyisocyanate” refers to non-aromatic polyisocyanates, i.e., acyclic aliphatic as well as cyclic aliphatic polyisocyanates.

Preferred water-soluble polyols have hydroxyl functionality from two to three, preferably two. Preferably, water-soluble polyols have a weight average molecular weight (M_(w)) in the range of from 900 to 16,000 Daltons, preferably 1,000 to 12,000, preferably 1,000 to 10,000. Preferred water-soluble polyols include polyethylene glycols and ethoxylated glycerol. Polyethylene glycols may include up to 15 wt % polymerized units of C₃-C₄ alkylene oxides, preferably no more than 10 wt %, preferably no more than 5 wt %, preferably no more than 2 wt %. Polyethylene glycols may include ethylene oxide polymers capped on one end with a C₁-C₄ alkyl group, preferably methyl. Preferably, polyethylene glycols have a weight average molecular weight (M_(w)) in the range of from 4,000 to 16,000 Daltons, preferably 4,000 to 12,000, preferably 6,000 to 10,000. An example of a suitable polyethylene glycol is PEG 8000, which is commercially available as CARBOWAX™ 8000 Polyethylene Glycol (a trademark of The Dow Chemical Company or its Affiliates). M_(w) is measured by the Size Exclusion Chromatography (SEC) method described below. Preferably, ethoxylated glycerol has M_(w) from 800 to 1600, preferably 1000 to 1400. In one preferred embodiment, the polymer further comprises polymerized units of polyethylene glycol mono-C₁-C₄ alkyl ethers along with a polyol having hydroxyl functionality from two to three.

Preferably, the calculated log P (cLogP) for the hydrophobic, terminal, or linker portion of the thickener is from −1.5 to 4.5; preferably −1.3 to 4.3 Preferably, the polyurethane thickener also comprises urea and/or biuret and/or allophanate groups. For example, urea groups form when reactants such as amines or water are used during the preparation of the polyurethane thickener.

Preferably, the water-soluble polyol has at least 90 wt % polymerized units of ethylene oxide, preferably at least 92 wt %, preferably at least 94 wt %, preferably at least 95 wt %.; preferably no more than 99.5 wt %, preferably no more than 99 wt %, preferably no more than 98.5 wt %. The percentage of polymerized units of ethylene oxide is calculated on a solids basis, i.e., the dry weight of the polymer without considering non-reactive solvents.

Preferably, the hydrophilic polyurethane polymer comprises from 0.5 to 5 wt % polymerized units of water-soluble polyols comprising polymerized units of a C₃-C₈ triol (e.g., glycerol, trimethylolpropane) and at least one of ethylene oxide, propylene oxide and butylene oxide; preferably from 1 to 4 wt %. Preferably, the water-soluble polyol has at least 75 wt % units of ethylene oxide, preferably at least 85 wt %.

Preferably, polyisocyanates have isocyanate functionality from two to five, preferably from two to four. Examples of suitable diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI) and its oligomers (e.g., 1,3,5-tris(6-isocyanatohexyl)1,3,5-triazine-2,4,6(1H,3H,5H)-trione (HDI trimer) and IPDI trimer), 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylene diisocyanate, 4,4′-methylenebis(isocyanatocyclohexane) (H12MDI), 2,4′-methylenebis(isocyanatocyclohexane), 1,4-cyclohexylene diisocyanate and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI).

A product of percent polymerized ethylene oxide units and polyethylene oxide mean molecular weight unexpectedly has been found to correlate with improved open time performance in the polyurethanes of the present invention. The polyethylene oxide (PEO) mean molecular weight is the weight average of the molecular weights (Mw) of the polyethylene oxide units in the polyurethane. For example, a polyurethane having equal weights of polyethylene oxides having Mw values of 8,000 and 2,000 has a polyethylene oxide mean molecular weight of 5,000. Preferably, the product of percent polymerized ethylene oxide units and polyethylene oxide mean molecular weight is at least 4,400, preferably at least 4,500, preferably at least 5,000, preferably at least 6,000; preferably no greater than 12,000, preferably no greater than 10,000, preferably no greater than 9,000.

The hydrophilic polyurethane may be prepared by contacting together under reactive conditions the water-soluble polyol, the aliphatic polyisocyanate and optionally, one or more of a diol mono-C₁-C₄ alkyl ether (e.g., a polymer of one or more of ethylene glycol, propylene glycol and butylene glycol end-capped with a lower alkyl group, preferably methyl) and a diamine, preferably an aliphatic diamine Preferably, at least one of the diamine and diol mono-C₁-C₄ alkyl ether is water soluble. Preferably, the diamine is a C₂-C₆ diamine, preferably C₂-C₄, preferably ethylene diamine The order of reactant charging may be varied as generally known for the synthesis of urethane polymers. For example, all of the reactants may be reacted together in a single synthesis step, or the reactants may be reacted in any synthetic sequence to achieve the desired final polymer. As is well known in the art of step growth polymerization to produce urethane polymers, the molar equivalent ratio of the ingredients is used to control such properties like molecular weight.

Preferably, M_(w) of the hydrophilic polyurethane polymer is at least 10,000, preferably at least 16,000, preferably at least 20,000, preferably at least 30,000; preferably no greater than 2,000,000, preferably no greater than 1,500,000, preferably no greater than 500,000, preferably no greater than 200,000.

Hydrophilic polyurethanes produced as described herein are not merely urethane polymers, but can further include combinations of allophanate branch points in the polymer backbone and urea linkages. The polymers may further include primary amine end groups or biuret branch points in the polymer backbone or a combination thereof.

The present invention is further directed to a latex paint comprising from 0.1 to 5 wt % of a the hydrophilic polyurethane of this invention.

Preferably, the latex paint comprises at least 0.2 wt % of the hydrophilic polyurethane, preferably at least 0.3 wt %, preferably at least 0.4 wt %, preferably at least 0.5 wt %; preferably no more than 4 wt %, preferably no more than 3 wt %. Percentages are based on the entire weight of the latex paint.

The present invention is further directed to a method for increasing open time in latex paint without substantial adverse effects on block resistance by adding the hydrophilic polyurethane in the aforementioned amounts.

EXAMPLES Example 1

A solution of polyethylene glycol (8200 g/mol, 75.4 g) in toluene (220 g) was dried by azeotropic distillation. After the solution was cooled to 90° C., DESMODUR N3600 (HDI trimer containing 70% trimer and smaller amounts of higher oligomers, overall NCO functionality=3.1) (1.37 g) and ethoxylated glycerol (1236 g/mol, 1.68 g) were added respectively, and the solution was stirred for 5 minutes. Bismuth octoate (0.19 g) was added to the solution, and the reaction mixture was stirred for 1 hour. The reaction mixture was cooled to room temperature, and the solvent was removed via rotary evaporation. The polymer was isolated as a white solid. 0.9 PEG8000/0.3667 N3600/0.2 Gly-EO (26). Mn=14,000; Mw=161,000

Example 2

A solution of polyethylene glycol (8200 g/mol, 82.2 g) in toluene (202 g) was dried by azeotropic distillation. After the solution was cooled to 90° C., ethylene diamine (0.075 g) was added, and the solution was stirred for 5 minutes. DESMODUR N3600 (1.68 g) and ethoxylated glycerol (1236 g/mol, 2.07 g) were added respectively, and the reaction mixture was stirred for another 5 minutes. Bismuth octoate (0.21 g) was added, and the reaction mixture was stirred for 1 hour. The reaction mixture was cooled to room temperature, and the solvent was removed via rotary evaporation. The polymer was isolated as an off-white solid. 0.8 PEG8000/0.1 ethylene diamine/0.3667 N3600/0.2 Gly-EO (26). Mn=13,000; Mw=1,300,000

Example 3

A solution of polyethylene glycol (8200 g/mol, 115.8 g) in toluene (216 g) was dried by azeotropic distillation. After the solution was cooled to 90° C., DESMODUR W (H12MDI 11.66 g) was added, and the solution was stirred for 5 minutes. Bismuth octoate (0.19 g) was added to the solution, and the reaction mixture was stirred for 1 hour. CARBOWAX MPEG2000 (2000 g/mol, 129.1 g) was added to the stirred reaction mixture, and the mixture was stirred at 90° C. for another hour. The reaction mixture was cooled to room temperature, and the solvent was removed via rotary evaporation. The polymer was isolated as a white solid. 0.35 PEG8000/1.1 DesW//0.8 MePEG2000. Mn=7,300; Mw=13,500

Example 4

A solution of polyethylene glycol (8200 g/mol, 76.6 g) in toluene (216 g) was dried by azeotropic distillation. After the solution was cooled to 90° C., DESMODUR H (HDI 4.94 g) was added, and the solution was stirred for 5 minutes. Bismuth octoate (0.19 g) was added to the solution, and the reaction mixture was stirred for 1 hour. Polyethylene glycol (8200 g/mol, 175.1 g) was added to the stirred reaction mixture, and the mixture was stirred at 90° C. for another hour. The reaction mixture was cooled to room temperature, and the solvent was removed via rotary evaporation. The polymer was isolated as a white solid. 0.35 E8000/1.1 HDI//0.8 PEG8000. Mn=96,000; Mw=188,000

Example 5

Polyethylene glycol (8200 g/mol, 1314.8 g) was mixed at 110° C. under full house vacuum in the Sigma batch melt reactor for 2 hours. After the reactor was cooled to 90° C. and purged with nitrogen, butylated hydroxytoluene (0.14 g) and ethylene diamine (1.2 g) were added respectively to the reactor, and the molten mixture was mixed for 5 minutes at 90° C. under nitrogen. DESMODUR N3600 (26.9 g) and ethoxylated glycerol (1236 g/mol, 33.0 g) were added respectively to the reactor, and the reaction mixture was mixed for an additional 5 min Bismuth octoate (3.3 g) was added to the reactor, and the reaction mixture was mixed for 10 minutes at 90° C. The resulting molten polymer was removed from the reactor and cooled to room temperature. 0.8 PEG8000/0.1 ethylene diamine/0.3667 N3600/0.2 Gly-EO (26). Mn=13,000; Mw=1,300,000

Example 6 Comparative

A solution of polyethylene glycol (4000 g/mol, 102.6 g) in toluene (287 g) was dried by azeotropic distillation. After the solution was cooled to 90° C., ethylene diamine (0.193 g) was added, and the solution was stirred for 5 minutes. DESMODUR N3600 (4.30 g) and ethoxylated glycerol (1236 g/mol, 5.28 g) were added respectively, and the reaction mixture was stirred for another 5 minutes. Bismuth octoate (0.26 g) was added, and the reaction mixture was stirred for 1 hour. The reaction mixture was cooled to room temperature, and the solvent was removed via rotary evaporation. The polymer was isolated as a white solid. 0.8 PEG4000/0.1 ethylene diamine/0.3667 N3600/0.2 Gly-EO (26)

Example 7 Comparative

A solution of polyethylene glycol (4000 g/mol, 73.6 g) in toluene (220 g) was dried by azeotropic distillation. After the solution was cooled to 90° C., DESMODUR N3600 (2.74 g) and ethoxylated glycerol (1236 g/mol, 3.36 g) were added respectively, and the solution was stirred for 5 minutes. Bismuth octoate (0.38 g) was added to the solution, and the reaction mixture was stirred for 1 hour. The reaction mixture was cooled to room temperature, and the solvent was removed via rotary evaporation. The polymer was isolated as a white solid. 0.9 PEG4000/0.3667 N3600/0.2 Gly-EO (26)

OT 1 d 1 d tack, Stain, % mins block, N N Leveling DE Tea Ex. 1 1 9.3 42 32 6.0 11.0 Ex. 2 1 9.1 28 25 5.4 16.8 Ex. 3 1 6.3 85 84 5.9 12.9 Control 1 5.1 65 87 6.0 9.7 OTE-500 1 9.4 104 125 4.2 18.2 OT is open time; 1 day block in Newtons; 1 d tack in Newtons; OTE-500 is a commercial open-time additive (RHODOLINE OTE-500 additive, Solvay, Inc.) which comprises nonionic and anionic sulfate ethoxylated tristyrylphenols; % of additive is based on entire weight of the latex paint.

While OTE-500 has good open time, it degrades block resistance, tack resistance, leveling, and stain resistance, while the polymers of this invention have good open time and less or minimal effect on block, tack, leveling, and stain compared to OTE-500. The product of Ex. 2 is found surprisingly to increase block and tack resistance compared to the control.

OT % mins Ex. 1 2 10 Ex. 2 2 11 Ex. 3 2 9.3 Ex. 4 2 12 Ex. 5 2 12.3 Ex. 6 2 5.0 Ex. 7 2 5.7 OTE-500 2 11

OT generally increases with increased level. However, OTE-500 often cannot even be used at 1% due to impairment of block and tack resistance, while PEU and PEUU can be used at higher level and therefore can practically increase open time compared to OTE-500.

EO mean PEO fraction × EO OT Ex. % PEO Mw mean Mw (2%) 1 98.25 8200 8057 10 2 97.96 8200 8033 11 3 95.47 4931 4708 9.3 4 98.08 8200 8042 12 5 97.96 8200 8033 12.3 6 96.00 4000 3840 5 7 96.56 4000 3862 5.7

Open time was measured in accordance with ASTM-D7488. Stain resistance studies were carried out by first applying the paint formulation to a white vinyl substrate with a 7-mil (0.18 mm) doctor blade. The film was allowed to stand for 7 days and the substrates were scanned using a calibrated flatbed scanner to obtain a baseline measurement. Stains were then applied to the dried film and allowed to set for 2 h before being subjected to the removal test: Leneta SC-1 non-abrasive media was combined with water (3:2 v/v) to form a solution. A thin film of the solution was applied to the stained coating; a non-abrasive sponge was dipped into the solution for 10 s, then contacted with the stained coating at a pressure of about 5 kPa and oscillated at 60 cycles/min (back and forth=1 cycle) for 100 s. The scrubbed substrates were rinsed with water and the stained substrates were imaged with the scanner to measure the root mean square difference in Lab coordinates between the baseline and the scrubbed stains (ΔE76).

Leveling drawdowns were made using a miniature analog of the Leneta Leveling Test Blade LTB-2. Drawdowns were dried horizontally under CTR conditions. Dried films were imaged and analyzed using custom-built software calibrated to mimic Leneta Drawdown Levelness Standards LS-2.

Coated samples were cured for 24 hr at 22° C. and 50% RH. A custom-built, automated, high throughput tribometer was used to measure tack. A Type 304 stainless steel ball, ⅜″ (9.5 mm) in diameter, was placed on the surface of the coating using 1 N of force. This force was applied for 5 s after which the force required to remove the ball from the surface was measured.

Coated samples were cured for 24 hr at 22° C. and 50% RH. Samples were precision cut to 0.5″×0.5″ (12.7×12.7 mm) with an Epilog Zing laser. Two coated samples were placed in contact with each other under a weight exerting 8 kPa of pressure for 30 min at 50° C. The force required to separate them was then measured using a TA-XT Plus Texture Analyzer. 

The invention claimed is:
 1. A hydrophilic polyurethane comprising polymerized units of: (a) a water-soluble polyol having hydroxyl functionality from two to four and a weight-average molecular weight from 4,200 to 16,000; and (b) an aliphatic polyisocyanate having isocyanate functionality from two to six comprising 1,6-hexamethylene diisocyanate or 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; and wherein polymerized ethylene oxide units comprise at least 85 wt % of said hydrophilic polyurethane; wherein a product of weight fraction of polymerized ethylene oxide units in the hydrophilic polyurethane and weight average of polyethylene oxide weight average molecular weight (M_(w)) is from 6,000 to 9,000.
 2. The hydrophilic polyurethane of claim 1 wherein M_(w) of the hydrophilic polyurethane is from 10,000 to 2,000,000.
 3. The hydrophilic polyurethane of claim 2 wherein polymerized ethylene oxide units comprise at least 90 wt % of said hydrophilic polyurethane.
 4. The hydrophilic polyurethane of claim 3 wherein the water-soluble polyol comprises: (i) a water-soluble polyethylene glycol having a weight average molecular weight from 4,200 to 10,000, and (ii) an ethoxylated glycerol having weight average molecular weight from 800 to 1,600.
 5. The hydrophilic polyurethane of claim 1 further comprising at least one of (i) a mono-C₁-C₄ alkyl ether of a polymer of one or more of ethylene glycol, propylene glycol and butylene glycol, and (ii) an aliphatic diamine.
 6. The hydrophilic polyurethane of claim 5 wherein the at least one of (i) a mono-C₁-C₄ alkyl ether of a polymer of one or more of ethylene glycol, propylene glycol and butylene glycol, and (ii) an aliphatic diamine is (ii) the aliphatic diamine.
 7. A latex paint comprising from 0.1 to 5 wt % of a hydrophilic polyurethane comprising polymerized units of: (a) a water-soluble polyol having hydroxyl functionality from two to four and weight-average molecular weight from 4,200 to 16,000; (b) an aliphatic polyisocyanate having isocyanate functionality from two to six comprising 1,6-hexamethylene diisocyanate or 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; and wherein polymerized ethylene oxide units comprise at least 85 wt % of said hydrophilic polyurethane; and wherein a product of weight fraction of polymerized ethylene oxide units and weight average of polyethylene oxide weight average molecular weight (M_(w)) is from 6,000 to 9,000.
 8. The latex paint of claim 7 wherein the water-soluble polyol comprises: (i) a water-soluble polyalkylene glycol having a weight average molecular weight from 4,200 to 10,000, and (ii) an ethoxylated glycerol having weight average molecular weight from 800 to 1,600.
 9. The latex paint of claim 8 wherein M_(w) of the hydrophilic polyurethane is from 10,000 to 2,000,000.
 10. The latex paint of claim 7 further comprising at least one of (i) a mono-C₁-C₄ alkyl ether of a polymer of one or more of ethylene glycol, propylene glycol and butylene glycol, and (ii) an aliphatic diamine.
 11. The latex paint of claim 10 wherein the at least one of (i) a mono-C₁-C₄ alkyl ether of a polymer of one or more of ethylene glycol, propylene glycol and butylene glycol, and (ii) an aliphatic diamine is (ii) the aliphatic diamine. 